Sulfurized phenolic materials

ABSTRACT

Organic material is stabilized by addition of a sulfurized product made by heating a mixture of (a) sulfur and (b) a reaction product formed by reacting in the presence of an alkali metal hydroxide catalyst (i) a mixture of at least two different alkylphenols, each having an unsubstituted ortho and/or para position, and (ii) formaldehyde. Preferably, the reaction product is formed in the presence of a small amount of primary lower alkanol such as methanol. When added to lubricating oil the sulfurized products also impart wear and corrosion inhibiting properties.

United States Patent 1 Malec et al.

[ SULFURIZED PHENOLIC MATERIALS [75] Inventors: Robert E. Malec,Birmingham;

Larry Plonsiter, Bloomfield Hills,

both of Mich.

[73] Assignee: Ethyl Corporation, Richmond, Va.

[22] Filed: Sept. 19, 1973 2 1] Appl. No.: 398,644

[56] References Cited UNITED STATES PATENTS 8/1916 McCoy 260/137 5/1950Smith et a1 260/l37 [451 May 13, 1975 Primary Examiner-Lewis GottsAssistant Examiner-D. R. Phillips Attorney, Agent, or Firm-Donald L.Johnson; Robert A, Linn; Joseph D. Odenweller [57] ABSTRACT Organicmaterial is stabilized by addition of a sulfurized product made byheating a mixture of (a) sulfur and (b) a reaction product formed byreacting in the presence of an alkali metal hydroxide catalyst (11 amixture of at least two different alkylphenols, each having anunsubstituted ortho and/or para position, and (ii) formaldehyde.Preferably, the reaction product is formed in the presence of a smallamount of primary lower alkanol such as methanol. When added tolubricating oil the sulfurized products also impart wear and corrosioninhibiting properties.

10 Claims, No Drawings 1 SULFURIZED PHENOLIC MATERIALS BACKGROUNDPhenolic antioxidants have been used to stabilize a broad range oforganic materials. For example, Coffield et al, U.S. Pat. No. 2,944,086,discloses the use of methylenebis (dialkylphenols) as antioxidants.Likewise, sulfur-bridged phenols have been used as antioxidants. Theseare made by reacting alkylphenols with sulfur halides (Coffield, US.Pat. No. 3,069,384).

SUMMARY According to the present invention, new antioxidants areprovided by heating a mixture of sulfur with a mixture ofmethylenebisphenols formed by reacting a mixture of alkylated phenolswith formaldehyde using a base catalyst and, optionally, an aliphaticprimary alkanol. When used in lubricating oil the new additives impartimproved wear and corrosion inhibiting properties in addition to beingeffective antioxidants.

DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of thisinvention is a sulfurized product made by the process comprising heatingto a temperature of about S200C. a mixture of (a) about 0.5-l0 parts byweight of sulfur and (b) about [00 parts by weight of a reaction productmade by reacting in the presence of an alkali metal hydroxide catalyst(i) 1 mole part of a mixture of alkylphenols containing at least twodifferent alkylphenols, each of said different alkylphenols having ahydrogen atom available in an ortho or para position, at least one ofsaid different alkylphenols having a tert-alkyl group in an orthoposition, and (ii) from about 0.3 to about mole parts of formaldehydeper equivalent of said alkylphenols.

The initial reaction product that is mixed with sulfur and heated toform the sulfur product can be made by known methods. lts preparation isdescribed in l-linkamp, US. Pat. No. 3,21 1,652, incorporated fullyherein by reference.

The initial reaction product comprises a mixture of methylenebisphenolscontaining (1) at least one symmetrical methylenebisphenol of theformula:

HO 0H wherein A is a tert-alkyl group having 4 to about l2 carbon atomsand B is selected from the group consisting of hydrogen and alkyl groupscontaining from 1-12 carbon atoms; and (2) at least one asymmetricalmethylenebisphenol having different phenol radicals and having at leastone ortho-tert alkyl group of from 4 to 12 carbon atoms.

The initial reaction product may be formed by mixing individualsymmetrical and asymmetrical methylenebis alkylphenols, each of saiddifferent alkylphenols having a hydrogen atom available in an ortho orpara position, at least one of said different alkylphenols having atertalkyl group in an ortho position, and (ii) from about 0.3 to about10 mole parts of formaldehyde per equivalent of said alkylphenol.

Examples of suitable alkylphenols having an unsubstituted ortho and/orpara position that can be used to prepare the initial reaction productinclude:

2-tert-butylphenol 2,6-di-tert-butylphenol 2,4-di-tert-butylphenol4-tert-butylphenol 2-isopropylphenol 2,6-diisopropylphenol2,4-diisopropylphenol 2-sec-butylphenol 2,6-di-sec-butylphenol2,4-di-sec-butylphenol 2-tert-hexylphenol 2,6-di-tert-hexylphenol2-tert-butyl-p-cresol 2-tertbutyl-o-cresol Z-tert-dodecylphenol2-tert-dodecyl-p-cresol 2-tert-decyl-o-cresol2-tert-butyl-6-isopropylphenol To prepare the initial reaction productone selects at least two different alkylphenols each having a hydrogenatom available at an ortho and/or para position and at least one ofwhich has an ortho-tert-alkyl substituent containing from 4 to about 12carbon atoms. This alkylphenol mixture is reacted with formaldehyde toform a mixture of symmetrical and asymmetrical alkylphenols. It ispreferred that the initial reaction product be formed by reacting in thepresence of an alkali metal hydroxide catalyst (i) 1 mole part of amixture of alkylphenols containing at least two different methylenebisalkylphenols.

The make-up of the mixtures of the phenols employed in preparing theinitial reaction product can vary over a wide range. Thus, as high as93-94 mole per cent of a first phenol and 6-7 mole per cent of a secondphenol may be used. Generally, at least 10 per cent of a phenoliccompound having a hydrogen in the ortho or para position, or both, and atertiary alkyl group of from 4-l2 carbon atoms ortho to the hydroxylgroup is employed. Thus, mixtures of from about 10-50 per cent of afirst phenol and 50-90 per cent of a second phenol are very useful inpreparing the initial reaction product.

In a more preferred embodiment the alkylphenol mixture comprises amixture of tert-alkyl-substituted phenols such as a mixture of two ormore of the followmg:

o-tert-butylphenol 2,6-di-tert-butylphenol 2,4-di-tert-butylphenolo-tert-amylphenol 2,6-di-tert-amylphenol 2,4-di-tert-amylphenolo-tert-hexylphenol 2,6-di-tert-hexylphenol 2,4-di-tert-hexylphenolo-tert-dodecylphenol 2,6-di-tert-dodecylphenol 2,4-di-tert-dodecylphenolIn a highly preferred embodiment the alkylphenol mixture comprises amixture of tert-butylphenols. In such mixtures it is preferred that oneof the phenols is 2,6-di-tert-butylphenol. Preferably, the mixturecontains at least 50 weight per cent 2,6-ditert-butylphenol and 530weight per cent 2-tert-butylphenol. Other constituents can include about3l5 weight per cent 2,4,o-tri-tert-butylphenol and small amounts of2,4-diten-butylphenol. Since 2,4,6-tri-tert-butylphenol does not containa reactive ortho or para hydrogen it does not enter into the initialreaction to form the mixture of methylenebis alkylphenols but itspresence in the resulting reaction product is not detrimental and, infact, contributes to the overall effectiveness of the final sulfurizedproduct.

In an especially preferred embodiment the mixture of phenols employed isthat obtained in an orthoalkylation reaction as described in Ecke etal., U.S. Pat. No. 2,831,898, incorporated herein by reference. In thisreaction a mixture consisting mainly of 2-tertbutylphenol,2,6-di-tert-butylphenol and 2,4,6-tri-tertbutylphenol is obtained byalkylating phenol with isobutylene using an aluminum phenoxide catalyst.Preferably, the alkylphenol mixture contains 50-90 weight per cent2,6di-tert-butylphenol, 5-30 weight per cent Z-tert-butylphenol andabout 3l5 weight per cent 2.4,G-tri-tert-butylphenol.

The initial reaction is readily carried out by mixing formaldehyde withthe mixture of alkylphenols and heating the mixture to reactiontemperature in the presence of a base catalyst such as an alkali metalhydroxide, for example, lithium hydroxide, sodium hydroxide or potassiumhydroxide.

The amount of formaldehyde should be an amount sufficient to form asubstantial number of methylene bridging groups. This amount isexpressed in terms of moles of formaldehyde per reactive phenolequivalents. The reactive phenol equivalent is determined by multiplyingthe moles of each individual phenol by the number of open ortho and/orpara positions in such phenol. For example. 1 mole of 2-tert-butylphenolrepresents two reactive phenol equivalents. Likewise, one mole of2,6-di-tert-butylphenol represents one reactive phenol equivalent, and 1mole of 2,4,o-tri-tert-butylphenol represents zero reactive phenolequivalents. Preferably, there should be used at least 0.3 mole offormaldehyde per reactive phenol equivalent. A useful range is fromabout 0.3 to l moles of formaldehyde per reactive phenol equivalent,although an amount in excess of this can be used.

The amount of base catalyst should be sufficient to cause the formationof methylene bridges at a reasonable rate. A useful range is from about0.01 to 0.25 mole of base per mole of alkylphenol. A preferred range isfrom 0.02 to 0.l mole of base per mole of alkylphenol. The preferredbase catalysts are sodium hydroxide and potassium hydroxide.

The initial reaction to form the mixture of symmetrical and asymmetricalmethylenebis alkylphenols can be carried out with or without a solvent.Preferably a solvent is used. Useful solvents include the secondary andtertiary alkanols such as isopropanol, sec-butanol and tert-butanol.

The initial reaction should be conducted at a temperature high enough topromote the reaction. A useful range is from 50 to about 200C. When asolvent is used it is convenient to conduct the initial reaction at thereflux temperature of the solvent. With isopropanol this is around 86C.

In a highly preferred embodiment the initial reaction is carried out inthe presence of an aliphatic primary lower alkanol. The presence of thisprimary alcohol tends to provide a more liquid final product byintroducing alkoxymethyl groups into the alkylphenols. More usefulprimary alcohols are those containing one to about 4 carbon atoms suchas methanol, ethanol, npropanol, n-butanol, and isobutanol. Of these,methanol is most preferred.

Only a small amount of aliphatic primary lower alkanol need be used toobtain excellent results. A useful range is from about 0.03 to 3.0 moleparts per each mole part of alkylphenol. A preferred range is from about0.03 to 0.3 mole parts per mole part of alkylphenol. Alternatively, theinitial reaction can be conducted using a primary aliphatic alcoholsolvent such as ethanol.

The following examples serve to illustrate the preparation of typicalinitial reaction products. All parts are by weight unless otherwisestated.

EXAM PLE l A mixture of weight per cent of 2,6-di-tertbutylphenol, 15weight per cent ortho-tertiary butylphenol and 10 weight per cent of2,4,6-tri-tertbutylphenol was reacted with paraformaldehyde in thepresence of ethanol. The following amounts of reactants were employed:

724 parts of phenol mixture 20 parts of potassium hydroxide 76 parts ofparaformaldehyde 600 parts of per cent ethanol The reaction wasconducted at reflux (8l83C.) for 2 hours after which time the mixturewas cooled to 70C. and neutralized with glacial acetic acid. The alcoholwas stripped under vacuum beginning at 70C. and ending at 35C. and 10mm. pressure. The residue was then dried with 1400 parts of benzene andwashed three times in 750 parts aliquots of water, dried and the benzenewas removed by vacuum distillation. The reaction product, a viscous oil,was found to be completely soluble and miscible with a hydrocarbonlubricating oil at up to 20 per cent weight concentration. The reactionproduct contains 4,4'-methylenebis-(2,6-di-tertbutylphenol), (3,5-di-tert-butyl-4-hydroxyphenyl)-( 3-tert-butyl-Z-hydroxyphenyl)-methane and(3,5-di-tertbutyl-4hydroxyphenyl)-( 3-tert-butyl-4-hydroxyphenyl)-methane as major components. In addition, the reactionmixture contains numerous other possible condensation products of2,6-di-tertbutylphenol and o-tert-butylphenol such as 4,4-methylenebis(Z-tert-butylphenol), 2,2- methylenebis(6-tert-butylphenol),(3-tertbutyl-2 hydroxyphenyl)-(3-tert-butyl-4-hydroxyphenyl)- methane,3-tert-butyl-4-hydroxybenzyl ethyl ether, 3-tert-butyl-2-hydroxybenzylethyl ether, the derivative of o-tert-butylphenol having ethyl ethersubstituents on methyl groups ortho and para to the hydroxyl groups, andvarious molecular weight polymers of the substituents present havingopen reactive ortho or para positions.

EXAMPLE 2 In a reaction vessel was placed 200 parts of isopropanol, 3.7parts of methanol, 9.5 parts of KOH and 270 parts of an alkylphenolmixture consisting essentially of 68 weight per cent2,6-di-tert-butylphenol, 22 weight per cent o-tert-butylphenol and 7weight per cent 2,4,o-tri-tert-butylphenol plus minor amounts of otheralkylphenols. The mixture was stirred at 60C. and 37.5 parts ofparaformaldehyde added. It was then heated to reflux (ca. 85C.) andstirred at reflux for 2 hours. Then 23.5 parts of acetic acid was addedand isopropanol distilled out up to a liquid temperature of 120C.Following this, 430 parts of toluene was added and the resultantsolution washed 4 times with I220 parts each of water. Toluene wasdistilled out up to a liquid temperature of l30C. at 120 mm Hg.

Other initial reaction products comprising mixtures of symmetrical andasymmetrical methylenebis alkylphenols can be prepared following theabove general procedure and those set forth in US. Pat. No. 3,2] l ,652.

The sulfurized product can be prepared by merely mixing elemental sulfurwith the initial reaction product and heating the mixture to atemperature sufficient to cause sulfurization. in general, a temperatureof about 50250C. is satisfactory, and a preferred temperature range isfrom about I20 to 180C.

The amount of sulfur used can vary widely. A useful range is from about0.5 l parts by weight of sulfur for each 100 parts by weight of initialreaction product. A preferred range is about 2-5 parts of sulfur per 100parts of initial reaction product. An amount in excess of this can beused and any unused portion removed by such means as filtration orcentrifugation.

The following examples illustrate the preparation of the sulfurizedproduct.

EXAMPLE 3 In a reaction vessel was placed 97 parts of the initialreaction product from Example 2, I00 parts of neutral mineral oildiluent and 3 parts of sublimed sulfur. The mixture was stirred andheated under a nitrogen atmosphere at l50-]65C. for 30 minutes. Theresultant sulfurized product was a clear yellow viscous liquid.

EXAMPLE 4 The procedure of Example 3 was repeated using 94 parts of theinitial reaction product of Example 2 and 6 parts of sulfur.

EXAMPLE 5 The procedure of Example 3 was repeated using 98 parts of thereaction product from Example 2 and 2 parts of sulfur.

EXAMPLE 6 The procedure of Example 3 was repeated except that themixture was stirred for l hour at l50l65C.

The sulfurized products of this invention are effective stabilizers in abroad range of organic materials of the type normally subject tooxidative deterioration in the presence of oxygen during use over anextended period. in other words, the organic compositions pro tected bythe present antioxidants are the type in which the art recognizes theneed for antioxidant protection and to which an antioxidant of some typeis customarily added to obtain an extended service life. The oxidativedegradation protected against is the slow gradual deterioration of theorganic composition rather than, for example. combustion. in otherwords, the present additives are not flame retarding additives nor flamesuppressing additives and the degradation protected against is notcombustion but, rather, the gradual deterioration of the organiccomposition due to the effects of oxygen over an extended period oftime.

Examples of organic materials in which the additives are useful includehomopolymers and copolymers of olefinically unsaturated monomers. forexample, poly' olefins such as polyethylene, polypropylene,polybutadiene, and the like. Also, poly-halohydrocarbons such aspolyvinyl chloride, polychloroprene, polyvinylidene chloride, polyfluoroolefins, and the like, are afforded stabilization. The additives provideboth antioxidant and antiozonant protection in natural and syntheticrubbers such as copolymers of olefinically unsaturated monomersincluding styrene-butadiene rubber (SBR rubber), ethylene-propylenecopolymers, ethylenepropylene-diene terpolymers such as the terpolymerof ethylene, propylene and cyclopentadiene or cyclooctadiene.Polybutadiene rubbers such as cispolybutadiene rubber are protected.Poly-2-chlorol ,3 butadiene (neoprene) and poly-2-methyl-l ,3- butadiene(isoprene rubber) are stabilized by the present additives. Likewise,acrylonitrile butadiene-styrene resins are effectively stabilized.Ethylene-vinyl acetate copolymers are protected, as arebutenemethylacrylate copolymers. Nitrogencontaining polymers such aspolyurethanes, nitrile rubber, and lauryl acrylate-vinylpyrolidonecopolymers are effectively stabilized. Adhesive compositions such assolutions of polychloroprene (neoprene) in toluene are protected. Fatsand oils of animal and vegetable origin are protected against gradualdeterioration. Examples of these are lard, beef tallow, coconut oil,safflower oil, castor oil, babassu oil, cottonseed oil, corn oil,rapeseed oil, and the like.

Petroleum oils and waxes such as solvent-refined midcontinentlubricating oil, microcrystalline wax, and gulf-coast lubricating oilsare effectively stabilized. Animal feeds such as ground corn, crackedwheat, oats, wheat germ, alfalfa, and the like, are protected by mixinga small but effective amount of the present addi tives with theseproducts. Vitamin extracts, especially the fat-soluble vitamins such asVitamins A, B, D, E and C, are effectively stabilized againstdegradation. The additives are useful in foamed plastics such asexpanded polystyrene, polyurethane foams, and the vari ous foamedrubbers, alkyd resins such as short oil terephthalicacid-glycerol-linseed oil resins, and typical long oil resins oftrimellitic acid-glycol-tung oil resins including epoxide-modified alkylresins. Epoxy resins themselves such asisopropylidenebisphenolepichlorohydrin epoxy resins are stabilizedagainst degradation.

Hydrocarbons such as gasoline, kerosene, diesel fuel, fuel oil, furnaceoil, and jet fuel are effectively protected. Likewise, synthetichydrocarbon lubricants, for example, a-decene trimer, polybutenelubricants, diand tri-C alkylated benzene and naphthalene syntheticlubricants are likewise protected.

Organometallics such as tetraethyllead, tetramethyl lead,tetravinyllead, ferrocene, methyl ferrocene, cyclopentadienyl manganesetricarbonyl, methyl cyclopentadienyl manganese tricarbonyl,cyclopentadie nyl nickel nitrosyl, and the like, are effectivelyprotected against oxidative degradation. Silicone oils and greases arealso protected.

Synthetic ester lubricants such as those used in turbines and turbojetengines are given a high degree of stabilization. Typical syntheticester lubricants include diQ-ethylhexyl sebacate, trimcthylolpropanetripelargonate, C aliphatic monocarboxylic esters of pentaerythritol,complex esters formed by condensing under esterifying conditionsmixtures of polyols, polycarboxylic acids, and aliphatic monocarboxylicacids and/or monohydric alkanols. An example of these complex esters isthe condensation product formed from adipic acid, ethyleneglycol and amixture of C aliphatic monocarboxylic acids. Plasticizers such asdioctyl phthalate are effectively protected. Heavy petroleum fractionssuch as tar and asphalt can also be protected should the need arise.

Polyamides such as adipic acid-l,6-diaminohexane condensates andpoly-o-aminohexanoic acid (nylon) are effectively stabilized.Polyalkylene oxides such as copolymers of phenol with ethylene oxide orpropylene oxide are stabilized. Polyphenyl ethers such aspoly-2,6dimethylphenyl ether formed by polymeriza tion of2,6-dimethylphenol using a coppenpyridine catalyst are stabilized.Polycarbonate plastics and other polyformaldehydes are also protected.

Linear polyesters such as phthalic anhydride-glycol condensates aregiven a high degree of protection. Other polyesters such as trimclliticacid-glycerol condensates are also protected Polyacrylates such aspolymethylacrylate and polymethylmethacrylate are effectivelystabilized. Polyacrylonitriles and copolymers of acrylonitriles withother olefinically unsaturated monomers such as methylmethacrylates arealso effectively stabilized.

The additives can be used to protect any of the many organic substratesto which an antioxidant is normally added. It can be used whereeconomics permit to protect such substrates as asphalt, paper,fluorocarbons such as teflon, polyvinyl acetate, polyvinylidene chloride, coumarone-indcne resins, polyvinyl ethers, polyvinylidene bromide,polyvinyl bromide, acrylonitrile. vinyl bromide copolymer, vinyl butyralresins, silicones such as dimethylsilicone lubricants, phosphatelubricants such as tricresylphosphate, and the like.

The additives are incorporated into the organic substrate in a small buteffective amount so as to provide the required antioxidant protection. Auseful range is from about 0.0] to about weight per cent, and apreferred range is from about 0.1 to 3 weight per cent.

Methods of incorporating the additive into the substrate are well known.For example, if the substrate is liquid the additive can be merely mixedinto the substrate. Frequently the organic substrate is in solution andthe additive is added to the solution and the solvent removed. Solidorganic substrates can be merely sprayed with a solution of the additivein a volatile solvent. For example, stabilized grain products resultfrom spraying the grain with a toluene solution of the additive. In thecase of rubbery polymers the additive can be added following thepolymerizstion stage by mixing it with the final emulsion or solutionpolymerization mixture and then coagulating or removing solvent torecover the stabilized polymer. It can also be added at the compoundingstage by merely mixing the additive with the rubbery polymer incommercial mixing equipment such as a Banbury blender. In this manner,rubbery polymers such as styrene-butadiene rubber, cispolybutadiene orisoprene polymers are blended with the antioxidant together with theother ingredients normally added such as carbon black, oil, sulfur, zineoxide, stearic acid, vulcanization accelerators, and the like. Followingmastication, the resultant mixture is fabricated and molded into afinished form and vulca nized. The following will serve to illustratethe manner in which the additives are blended with various organicsubstrates.

EXAMPLE 7 To a synthetic rubber master batch comprising lOO parts of SBRrubber having an average molecular weight of 60,000, 50 parts of mixedzinc propionate stearate, 50 parts of carbon black, 5 parts road tar, 2parts sulfur and 1.5 parts of mercapto benzothiazole is added 1.5 partsof the additive of Example 3. After mastication, the resultant masterbatch is cured for of) minutes using 45 psi steam pressure, resulting ina stabilized SBR vulcanizate.

EXAMPLE 8 A synthetic SBR polymer is prepared by polymerize ing 60 percent styrene and 40 per cent butadiene in an aqueous emulsion employinga sodium oleate emulsifier and a peroxide catalyst. Following this,sufficient additive of Example 4 is added to provide 0.3 weight percent, based upon the SBR polymer. The emulsion is then coagulated usingan acidified salt solution and the coagulated polymer compressed intobales for stor age. The polymer is stable during storage and can laterbe compounded to prepare SBR vulcanizatcs.

EXAMPLE 9 One part of the additive of Example 5 is blended with [00parts of raw butyl rubber prepared by the copolymerization of per centisobutylene and l0 per cent isoprene, resulting in a stable elastomer.

EXAMPLE 10 A cis-polybutadiene polymer is prepared having 90 per centcis configuration by polymerizing butadiene in a toluene solventemploying a diethyl aluminum chloridecobalt iodide catalyst. Followingthe polymerization, a small amount sufficient to provide 0.2 weight percent of the additive of Example 6 is added to the toluene solution,following which the solution is injected into boiling water togetherwith steam causing the solvent to distill out and the cis-polybutadieneto coagulate, forming a rubber crumb. The crumb is dried and compressedinto bales, resulting in a stabilized cis polybutadiene.

EXAMPLE ll A butadiene-acrylonitrile copolymer is prepared from1,3-butadiene and 32 per cent of acrylonitrile. One percent, based onthe weight of polymer, of the additive of Example 3 is added as anemulsion in a sodium oleate solution. The latex is coagulated and thecoagulum is washed and dried, resulting in a stabilizedbutadiene-acrylonitrile copolymer.

EXAMPLE 12 To L000 parts of a solid polypropylene powder is added 5parts of the additive of Example 4 and l0 parts ofdilaurylthiodipropionate. The mixture is heated to its melting point andrapidly stirred and extruded to form a useful polypropylene filament.

EXAMPLE 13 To [,000 parts of polyethylene is added 3 parts of theadditive of Example and 5 parts of dilaurylthiodipropionate. The mixtureis heated to its melting point and stirred and then passed through anextruder having a central mandrel to form tubular polyethylene which isinflated to form a useful polyethylene film.

EXAMPLE 14 To 100,000 parts of a midcontinent, solvent-refined mineraloil having a viscosity at 100F. of 373.8 SUS and at 210F. of 58.4 SUS isadded 500 parts of the additive of Example 6. Following this is added100 parts of a zinc dialkyldithiophosphate, 50 parts of an overbasedcalcium alkaryl sulfonate, 1,000 parts of a poly dodecylmethacrylateV.l. improver and 2,000 parts of a 70 per cent active oil solution of analkenyl succinimide of tetraethylenepentamine in which the alkenyl grouphas a molecular weight of 950. The resultant mixture is blended whilewarm, following which it is filtered and packaged, giving a stablelubricating oil useful in automotive engines.

EXAMPLE 15 To 10,000 parts of a dimethyl silicone lubricating oil isadded 50 parts of the additive of Example 3. The mixture is stirred at50C. until thoroughly blended, re sulting in a stable siliconelubricating oil.

EXAMPLE 16 To 10,000 parts of corn oil is added 15 parts of the additiveof Example 4. The mixture is stirred, giving a corn oil highly resistantto normal oxidative degradation.

EXAMPLE 1? To [0,000 parts of trimethylolpropane tripelargonate is added200 parts of tricresylphosphate, 10 parts of di' methyl silicone, 10parts of benzothiazole, 50 parts of phenyl-B-naphthyl amine, and 50parts of the additive of Example 5, resulting in a stabilized syntheticester lubricant.

EXAMPLE l8 Wax paper is made by impregnating paper with paraffin waxcontaining 0.05 weight per cent of a mixture of the additive of Example6. The wax paper is used to make containers for potato chips whichresults in chips having extended shelf life.

EXAMPLE 19 To 10,000 parts of gasoline having an 87 R.O.N. is added 20parts of the additive of Example 3 and suffcient commercialtetraethyllead antiknock fluid to provide 2.5 grams of lead per gallon,resulting in a stabilized gasoline having a 96 RON.

EXAMPLE 20 To 10,000 parts of4l cetane diesel fuel is added 50 parts ofhexyl nitrate and parts of the additive of Example 4, providing a stablediesel fuel.

EXAMPLE 21 To 10,000 parts of melted lard is added 10 parts of theadditive of Example 5 and the mixture is stirred until thoroughlyblended, resulting in a lard highly resistant to normal oxidativedegradation.

From the foregoing, it should be apparent how to prepare stable organiccompositions using the additives of this invention.

Tests were carried out in mineral lubricating oil to measure the Wearinhibiting properties of the sulfurized product compared to theunsulfurized initial reaction product. These were four-bal! wear testsin which the central ball of a four-ball pyramid is rotated under a 50Kg load for 1 hour against the three stationary balls. The balls arelubricated with mineral oil at 1 10C. containing the test additive. Therotating ball causes a circular scar to form on the three fixed balls.The average diameter of this scar is a measure of the amount of wear.Results obtained using lubricants containing the present sulfurizedproducts compared to the unsulfurized initial reaction products areshown in the following table.

The above results testify to the exellent wear inhibiting properties ofthe present sulfurized products. The additives of Examples 3-6significantly reduced the amount of wear compared to that obtained withthe non-sulfurized reaction product of Example 2.

Further tests were carried out to determine the antioxidanteffectiveness of the sulfurized product. In these tests ml mineral oilsamles were prepared and a clean, weighed copper-lead bearing placed ineach sample. The test additive was added and the oil maintained at 325F.for 96 hours while bubbling air through it at a rate of 48 l/hour. Atthe end of this time the amount of sludge formed was rated visually andthe bearing weighed to determine bearing weight loss. The resultsobtained with the sulfurized product compared to the unsulfurizedinitial reaction product of Example 2 and a nonadditive control were asfollows:

Small weight gain A is no sludge In the above table the concentration ofadditives of Examples 3, 5 and 6 was the same as that of Example 2because the additive of Examples 3, 5 and 6 is diluted with oil to 50per cent active ingredient. The results show that the sulfurized productretained the excellent antioxidant effectiveness of the initial reactionproduct and, in fact, had a cleaner sludge rating.

The lubricating oil compositions are prepared by blending a sulfurizedproduct of this invention with lubricating oil including both syntheticoils and mineral oils. Suitable synthetic oils include synthetic esterssuch as esters of alkanols and alkane polyols (pentaerythritol,trimethylolpropane, and the like), complex esters made using monoandpoly-carboxylic acids and mnoand poly-hydroxy alkanols, polyolefin oilssuch as liquid polybutene. silicon oils, silicate esters, polyphenyleneoxide oils. and the like. Preferably the oil is a mineral lubricatingoil. The amount of sulfurized product should be an amount adequate toimpart the desired degree of antiwear and antioxidant properties. Goodresults can be obtained using from 0.1 to about weight per cent. Apreferred range is from 03 to about 3 weight per cent.

Other additives normally added to lubricating oil can be included in theformulated oil. These include metal sulfonates such as calciumalkarylsulfonates and magnesium alkarylsulfonates. ZlflCdialkyldithiophosphates. antioxidants such as4.4-methylenebis(2,6-di-tertbutylphenol), viscosity index improvers suchas poly-laurylmethacrylates. polybutenes and ethylenepropylenecopolymers. Likewise. metal phenates such as barium or zincalkylphenates or sulfur-bridged metal phenates may be included.Phosphosulfurized hydrocarbons and their metal salts may be added suchas the reaction product of P 8 with terpenes or polybutenes and theirbarium salts. Ashless dispersants such as the high molecular weight{800-3000} alkylsuccinimides of ethylenepolyamines are very beneficial.Also. high molecular weight (800-3000) alkylphenolformaldehyde-amineleg. N.N-dimethyl-l .3- propanediamine or tctraethylenepentamine)Mannich condensation products are useful dispersants in the lubricatingoil compositions of this invention.

We claim:

I. A sulfurized product made by the process comprising heating to atemperature of about 50-200C a mixture of (a) about 0.5-l 0 parts byweight of sulfur. and (bl about 100 parts by weight of a reactionproduct. said reaction product comprising a major amount of a mixtureofmethylenebis phenols, said mixture comprising l l a substantial amountof at least one symmetrical methylenebis phenol having identicallysubstituted phenol radicals and having the formula:

wherein A is a tert-alkyl group having from 4 to about l2 carbon atomsand B is selected from the group consisting of hydrogen and alkyl groupshaving 1-12 carbon atoms, and (2) a substantial amount of at least oneasymmetrical methylenebis phenol having different phenol radicals andhaving at least one ortho-tert-alkyl group containing from 4-l2 carbonatoms. said reaction product being made by reacting in the presence ofan alkali metal hydroxide catalyst (i) one mole part of a mixture ofalkyl phenols. said mixture containing at least two different alkylphenols. each of said different alkyl phenols having a hydrogen atomavailable in an ortho or para position. said different alkyl phenolsbeing selected from the group consisting of Z-alkyl phenols. 2.6-dialkylphenols and 2.4-dialkyl phenols wherein said alkyl groups contain l-l2carbon atoms. the remaining components of said mixture consisting mainlyof 2,4,6-tri-alkyl phenol wherein said alkyl groups contain [-12 carbonatoms. at least one of said different alkyl phenols having a tert-alkylgroup con taining 4-12 carbon atoms in an ortho position. and {ii} fromabout 0.3 to about l0 mole parts of formaldehyde per equivalent of saidalkyl phenols.

2, A sulfurized product of claim 1 wherein said reaction product isformed in the presence of from about 0.03 to 3.0 mole parts of a primarylower aliphatic alcohol containing l to about 4 carbon atoms.

3. A sulfurized product of claim I wherein said mixture of alkylphenolscomprises a mixture of tort butylphenols.

4. A sulfurizcd product ofclaim 3 wherein one ofsaid differentalkylphenols is 2.6-di-tert-butylphenol.

5. A sulfurized product of claim 4 wherein one of said differentalkylphenols is Z-tert-butylphenol.

6. A sulfurized product of claim 5 wherein said reaction product isformed in the presence of from about 0.03 to about 0.3 mole parts of aprimary lower aliphatic alcohol containing l to about 4 carbon atoms.

7. A sulfurized product of claim 5 wherein said mixture of alkylphenolscomprises about 50-90 weight per cent 2.6-di-tert-butylphenol and 5-30weight per cent 2-tert-butylphenol.

8. A sulfurized product of claim 7 wherein said reaction product isformed in the presence of from about 0.03 to 0.3 mole parts of a primarylower aliphatic alcohol containing 1 to about 4 carbon atoms.

9. A sulfurized product of claim 8 wherein said pri mary lower aliphaticalcohol is methanol.

10. A sulfurized product of claim 9 wherein said mixture of alkylphenolsconsists mainly of about 50-90 weight per cent 2,o-di-tert-butylphenol.about 5-30 weight per cent 2-tert-butylphenol and about 3-15 weight percent 2,4,6-tri-tert-butylphenol.

1. A SULFURIZED PRODUCT MADE BY THE PROCESS COMPRISING HEATING TO ATEMPERATURE OF ABOUT 50*-200*C A MIXTURE OF (A) ABOUT 0.5-10 PARTS BYWEIGHT OF SULFUR, AND (B) ABOUT 100 PARTS BY WEIGHT OF A REACTIONPRODUCT, SAID REACTION PRODUCT COMPRISING A MAJOR AMOUNT OF A MIXTURE OFMETHYLENEBIS PHENOLS, SAID MIXTURE COMPRISING (1) A SUBSTANTIAL AMOUNTOF AT LEAST ONE SYMMETRICAL METHYLENEBIS PHENOL HAVING IDENTICALLYSUBSTITUTED PHENOL RADICALS AND HAVING THE FORMULA:
 2. A sulfurizedproduct of claim 1 wherein said reaction product is formed in thepresence of from about 0.03 to 3.0 mole parts of a primary loweraliphatic alcohol containing 1 to about 4 carbon atoms.
 3. A sulfurizedproduct of claim 1 wherein said mixture of alkylphenols comprises amixture of tert-butylphenols.
 4. A sulfurized product of claim 3 whereinone of said different alkylphenols is 2,6-di-tert-butylphenol.
 5. Asulfurized product of claim 4 wherein one of said different alkylphenolsis 2-tert-butylphenol.
 6. A sulfurized product of claim 5 wherein saidreaction product is formed in the presence of from about 0.03 to about0.3 mole parts of a primary lower aliphatic alcohol containing 1 toabout 4 carbon atoms.
 7. A sulfurized product of claim 5 wherein saidmixture of alkylphenols comprises about 50-90 weight per cent2,6-di-tert-butylphenol and 5-30 weight per cent 2-tert-butylphenol. 8.A sulfurized product of claim 7 wherein said reaction product is formedin the presence of from about 0.03 to 0.3 mole parts of a primary loweraliphatic alcohol containing 1 to about 4 carbon atoms.
 9. A sulfurizedproduct of claim 8 wherein said primary lower aliphatic alcohol ismethanol.
 10. A sulfurized product of claim 9 wherein said mixture ofalkylphenols consists mainly of about 50-90 weight per cent2,6-di-tert-butylphenol, about 5-30 weight per cent 2-tert-butylphenoland about 3-15 weight per cent 2,4,6-tri-tert-butylphenol.